Anthraquinone acridone carbazoles in which the acridone nucleus is linked to the carbazole nucleus through an amide linkage



,quinonenucleus lby an amide linkage. compounds are capable. of dyeing vegetable fibers Patented Apr. 19, 1 949 ANTHRAQUINONE ACRIDONE CARBAZOLES WHICH THE- ACRIDONE NUCLEUS'IS LINKED TOITHE CARBAZOLE NUCLEUS THROUGH AN AMIDE- LINKAGE 1 Fritz Max, -Easton,*"Pa., and David I. Randall, =Phillipsburg, N.= J assignors to General Aniline & Film Corporation, New'York, N. Y.,' a corporation of Delaware 7 No Drawing. -Applica'tion December 12, 1946, Serial No. 715,653

3 Claims. 1

The present invention relates to anthraquinone acridone carbazole dyes and more. particularly to such dyes in which the acridone nucleus is linked through the 6 position to the 1 position of the carbazole anthraquinone nucleus by an amide linkage.

It has been proposed in the past to produce anthraquinone acridone carbazoles for use as vat dyes. The reported compounds, however, are such that the acridone nucleus is joined to the carbazole nucleus through condensed ring systems.

We have now found a new class of anthraquinone acridone carbazoles in which the anthraquinone acridone nucleus is linked in the 6 position to the 1" position of the carbazole anthra- These in deep shades ranging from brown, pa-rticu1arly red-brown, to grayzshades of excellent fastness I proper-ties.

It is" accordingly an object of the persent invention to produceianthraquinone acridone carbazoles in which the acridonenucleus is linked to the carbazole nucleus through an amide linkage.

-A further'object'of the present invention are anthraquinone acridone carbazoles capable of dyeing vegetable fibers in pleasing deep shades'of brown to gray in which the acridonenucl'e'us is linked to the carbazole nucleus through an amide linkage.

*A further object of the present invention are anthraquinone'acridone carbazoles in which the acridone nucleus is linked in 6'-'position to the,

1"-position of the carbazole anthraquinone nucleus by an amide linkage.

Other and further 'importantobjects 1 of the invention will become apparent as the description proceeds.

The compounds the preparation and useof -which are contemplated" herein may be depicted by the following structural formula:

like, aryl such as phenyl, naphthyl and the like, or halogen such as chlorine, bromine, fluorine and the like, and Y is hydrogen or a benzoylamino radical: such as benzoylamino, p-methoxy benzoylamino, p-chlorobenzoylamino, p-rnethyl benzoyla'mino and the like.

The above products are obtained by condensing an anthraquinone-2.l-(N) -1.2'-(N) -6- (o-ihalogen benzoylamido) -benzacridone with a 1- amino anthraquinone which may bear abenzoylamino radical in the 4- or 5- position and ring closing the. resulting product. The condensation is effected by heating the reactants to a temperature ranging from about to 250 C. in the presence. of an acid acceptor such as soda ash, potassium carbonate, sodium acetate and the like, and copper or a salt of copper such as copper acetate and the like. Suitable benzacridones for use in the condensation are:

befiz'oylamido) -benzacridone,

'An-tlrraquinone 2.1-(N) -1'.2-(N) -3'-chloro-6'- :(o-chlorbenzoylamido) -benzacridone,

6' (o-chlorbenzoylamido) -'benzacridone. Anthraquinone2.l- (N) 1'.2'--(N)' -3'-methoxy-6' (o-chlorbenzoylamido) --benzacridone, Anthraquinone-2.1-(N) -1.2' (N) -3'-phenyl-6- (o-chlorbenzoylamido) -benzacridone, Anthraquinone 2.1 (N) -1'=.2 '-(N)-3'-phenoxy- 6'- (o-chlo rbenzoylamidm -benzacridone, Anthraquinoire-ZLl-(N) -1 '.2'- (N) -3-bromo -6' (o-chlorbenzoylarnido) benzacridone, Anthraquinone=2.l- (N) -1".2' (N) -3'.4' dimethoxy-G'='(o=chlorbenzoylamido) -ben'zacridone, Anthraquinone-ll- (N) -1 .2 (N) -%"-'-phenyl 6- (o-chlorbenzoylamido) '-benz'acridone, Anthraquinone- 2.1 (N) -1'.2'-(N) -3-ethyl-6 (o-chlorbenzoylamido) -ben'zacrido ne, Anthraquinone-2.1- (N) -1.2'- (N) 3 .4'-dimethyl- 6'- (o-chlorbenzoylamido) -benzacridone, Anthraquinone ll-(N) 1'.2"-('N) -l-propyl 6- (o-chlorbenzo'ylamido)-benzacridone, and the like.

Suitable l-amino anthraquinones arei l-amino' anthraquinone 1-amino-4-benzoylamino anthraquino'ne I-amino-S-benzdylarhino' anthraquinone 1 -amino-4-p-me'thy1 benzoylamino anthraquinone 1-amino-5-p-chlorcbenzoylamino anthraquinone 3 4 l-amino-fi-p-methoxy benzoylamino anthraqui- 3. The compound is the same as that of Fornone and the like. mula 1 excepting that the 3'-position is unsubstituted.

4. The compound is the same as that of For- 5 mula 1 excepting that the 7-position is unsubstituted.

5. The compound is the same as that of Formula 2 excepting that the 4-position is substituted by methoxy.

The ring closure of the condensation product of the 'benzacridone and the l-amino anthraquinone is efiected by heating the intermediate condensation product to a temperature of about 50 to 125 C. in the presence of an acid condensing agent. The acid condensing agent may be an acid such as concentrated sulfuric acid, chlor- 1o sulfonic acid and the like, but We prefer to em- The compound the Same that} P ploy an acid-reacting metal chloride in the presmula} exceptmg that the and 4 P are ence of a non-basic organic solvent. As metal Substltuted by Chlorochlorides there may be used aluminum chloride, The compound is the Same as that of F ferric chloride and the like. Suitable non-basic mule 2 excepting that the 3- and 4- positions organic solvents are nitrobenzene, toluene, di- 15 are Sub t ted by chlm'o.

nitrobenzene, tetrachlorethane, chlorbenzene, etc. The compound is the same as that of For- The course of the reaction, while utilizing as mula 1 excepting that the 3-position is substithe parent materials, anthraquinone-2.1-(N)- tuted by phenyl. 1'.2-(N) -3-chloro-6-(o-chlorbenzamido)-benz- 9. The compound is the same as that of Foracridone and 1-amino-5-benzoylamino anthramula 2 excepting that the 3-position is substiquinone is illustrated by the following equation: tuted by phenoxy.

0 NHCOCQH; 01- H N-(: NH-C H "Q "Q 0 A101, 0 I n EN \o \0 I 0 NBC 0 OBHB 6 NBC 0 CIHB Examples of compounds embraced by the above 10. The compound is the same as that of Forgeneral formula are the following. For the sake mula 1 excepting that the 3-position is substi- 0f brevity, the nomenclature subsequently emted by bromine. ployed is based on the formulae given. 11. The compound is the same as that of For- L mula 1 excepting that the 4-position is substi- Cl tuted by phenyl.

12. The compound is the same as that of For- H NH-(fi mula 1 excepting that the 3-position is substituted by ethyl. EN 13. The compound is the same as that of For- 0 o\ mula 2 excepting that the 3- and 4'-positions ,are' substituted by methyl.

14. The compound is the same as that of For- \0 mula 1 excepting that the 4-position is substi- 0 tuted by propyl.

o NHCOCoHs The following examples serve to illustrate the invention, the parts being by Weight unless otherwise stated. It is understood that the following are exemplary and not limitative of the invention.

9.6 parts of the above condensation product are dissolved in a solution of 36 parts of anhydrous aluminum chloride and 145 parts of nitrobenzene and stirred while heating to 50 C. for 3 hours. The reaction mixture is poured into dilute hydrochloric acid, the nitrobenzene is removed by steam distillation, and the dyestuff is isolated by filtration. Cotton is dyed by the product from a hydrosulfite vat in bright red-brown shades of excellent fastness properties.

Example II The procedure is the same as in Example I excepting that the 1-amino-5-benzamido anthraquinone is replaced by l-amino--benzamido anthraquinone.

Example III The procedure is the same as that of Example I excepting that the l-amino-5-benzamido anthraquinone is replaced by l-amino-anthraquinone.

Example IV Examlple V A mixture of 7.2 parts of anthraquinone-2.1-(N) -l.2-(N) 3'-methoxy-6-(o-chlorbenzamid-o) benzacridone 4.2 parts of 1-amino-4-benzamino anthraquinone 4 parts of soda ash 1 part of copper acetate, and

108 parts of nitrobenzene are heated at 205 C. for 15 hours. The dark precipitate which results is removed by filtration, washed with ethanol, dilute hydrochloric acid and water. The dyestuff yields strong blue gray dyeings on cotton from a violet vat.

To effect carbazolation,

7 parts of the above condensation product are dissolved in a solution of 33 parts of aluminum chloride in 120 parts of nitrobenzene and the solution stirred for 3 hours while heating the same to 50 C. The dyestuff is then isolated as in Example I. The product dyes cotton powerful violet gray shades from a violet vat, the dyeings possessing excellent fastness properties.

Example VI The procedure is the same as that of Example V excepting that the anthraquinone-(N)-1.2'- (N) -3-methoxy-6'-(o-chlorbenzamido) benzi a O HN I fi:

. 1/ O I] }o acridone is replaced by the corresponding 3- ethyl derivative.

Modifications of the invention will occur to persons skilled in the art and I therefore do not 5 intend to be limited in the patent granted except as required by the prior art and the appended claims.

We claim:

1. Vat dyes having the following formula:

wherein X is a member selected from the class consisting of hydrogen, alkyl, alkoxy, aryl, any]- oxy and halogen and Y is a member selected from the class consisting of hydrogen and a benzamido radical.

2. A vat dye of the following formula:

I ll 0 EN 5 n 0 r O 0 t) NHOOOeHa capable of dyeing cotton from a hydrosulfite vat in bright red-brown shades of excellent fastness properties.

3. A vat dye of the following formula:

NHCOCBH5 which dyes cotton from a hydrosulfite vat in beautiful violet-gray shades of excellent fastness properties.

FRITZ MAX. DAVID I. RANDALL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number 

